EP1171664B1 - Method for colouring a transparent article made of polycarbonate and resulting article - Google Patents

Method for colouring a transparent article made of polycarbonate and resulting article Download PDF

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Publication number
EP1171664B1
EP1171664B1 EP00917114A EP00917114A EP1171664B1 EP 1171664 B1 EP1171664 B1 EP 1171664B1 EP 00917114 A EP00917114 A EP 00917114A EP 00917114 A EP00917114 A EP 00917114A EP 1171664 B1 EP1171664 B1 EP 1171664B1
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EP
European Patent Office
Prior art keywords
article
anyone
layer
thickness
colouring agent
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EP00917114A
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German (de)
French (fr)
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EP1171664A1 (en
Inventor
Gilles Baillet
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EssilorLuxottica SA
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Essilor International Compagnie Generale dOptique SA
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/20—Physical treatments affecting dyeing, e.g. ultrasonic or electric
    • D06P5/2005—Treatments with alpha, beta, gamma or other rays, e.g. stimulated rays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/16—Surface shaping of articles, e.g. embossing; Apparatus therefor by wave energy or particle radiation, e.g. infrared heating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/0007—Manufacturing coloured articles not otherwise provided for, e.g. by colour change
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/004—Dyeing with phototropic dyes; Obtaining camouflage effects
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/0827—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using UV radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B29K2995/002—Coloured
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2011/00—Optical elements, e.g. lenses, prisms
    • B29L2011/0016—Lenses
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/34—Material containing ester groups
    • D06P3/52—Polyesters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/93—Pretreatment before dyeing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/933—Thermosol dyeing, thermofixation or dry heat fixation or development
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31507—Of polycarbonate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31935—Ester, halide or nitrile of addition polymer

Definitions

  • the present invention relates generally to a process for coloring a transparent polycarbonate article, by example an optical or ophthalmic article, and in particular a lens.
  • PC Polycarbonate
  • Ophthalmic lenses made of conventional organic material such as that the material obtained by polymerization of diallylcarbonate diethylene glycol, are usually colored by soaking in baths aqueous dispersed dyes, the baths being maintained at a temperature of the order of 95 ° C.
  • Such a process cannot be directly transposed to coloring polycarbonate articles, for example a polycarbonate lens.
  • Document US Pat. No. 5,443,597 describes a method for coloring a article, such as an optical element, formed from a copolymer polycarbonate-polyester, which consists in subjecting the copolymer to a UV irradiation of predetermined intensity, for a period predetermined, then subjecting the article to a coloring treatment, by example by soaking in an aqueous solution of a dye.
  • the presence of polyester chains in the backbone of the copolymer is essential because it is the polyester bond which is ruptured by irradiation and which allows subsequent penetration of the dye.
  • the penetration depths of the pigments are weak, about 10 to 15 nm. To get more penetration important, the document teaches that the copolymer must then contain a higher proportion of polyester.
  • Document JP 1-118682-A describes a process for coloring surface of a polycarbonate film which includes irradiation for 262 hours from the surface of the film by UV radiation then immersion of the film in dye solution for 17 hours.
  • this process particularly intended for the coloring of PC ophthalmic lenses, in particular lenses for glasses, must not only be simple but allow a coloring of the lenses at the customer's request.
  • shade A (light), shade B (medium), shade C (dark).
  • the process must not significantly alter the essential properties of the lens such as transparency, impact and scratch resistance.
  • the coloration obtained must be stable over time.
  • An article in PC thus treated can be colored with ease, in particular by means of aqueous dispersions and solutions of dyes and pigments.
  • the process of the invention can also understand the irradiation of the item to cause a photodegradation of polycarbonate material from two opposite sides of the article, (each side then being subjected to photodegradation) to form in the article two photodegraded surface layers of the polycarbonate material each having a thickness of at least 1 to 2 ⁇ m.
  • the two sides of the article are then placed contact with the coloring agent to spread the coloring agent in a thickness of at least 1 ⁇ m, preferably at least 2 ⁇ m, for each of the two layers photodegraded surface.
  • the thickness of the surface layer photodegraded or photodegraded surface layers will be 2 to 20 ⁇ m, and better from 2 to 10 ⁇ m.
  • the coloring agent can be diffused throughout the thickness of the photodegraded surface layer (s).
  • the UV radiation from the photodegradation step by irradiation has a wavelength spectrum such that, during irradiation, at least 50%, preferably at least 60%, and better still, at least 65% of l the irradiation energy comes from part of the radiation with a wavelength ⁇ 320 nm.
  • the irradiation energy of the article due to the part of the UV radiation of wavelength ⁇ 320 nm is 2.4 to 48 J / cm 2 , better still 10 to 30 J / cm 2 , however that the irradiation energy of the article due to the part of the UV radiation of wavelength> 320 nm is from 0.9 J / cm 2 to 15 J / cm 2 , better of 2 J / cm 2 to 8 J / cm 2 .
  • UV radiation has a wavelength spectrum ranging from 200 to 400 nm).
  • the duration for which each point of one of the faces of the lens is subjected to the irradiation is less than 10 minutes, preferably less than 2 minutes and better still less than 30 seconds.
  • the optimal duration of the photodegradation step during which the energies mentioned above are received by the lens varies from 0.1 to 10 seconds, generally and preferably from 0.4 to 4 seconds.
  • UV radiation suitable for the process of the invention can be obtained, for example using a UV lamp “H” from the Company FUSION UV SYSTEM at 50% of its nominal power or one UV lamp “D” from the same company at 40% of its nominal power.
  • the irradiation UV of the polycarbonate article should be such that photoaging essentially proceeds according to an "intrinsic" photochemistry, that is to say a surface attack. So, we can get an article in material polycarbonate having a photodegraded surface layer improving the ability to color the article without harming other properties optical and mechanical of the polycarbonate material.
  • the polycarbonates suitable for the present invention are all polycarbonates not containing polyester units.
  • Polycarbonate is understood in the present invention, also homopolycarbonates as well as copolycarbonates and block copolycarbonates, it being understood that the copolycarbonates with polyester motifs are excluded.
  • polycarbonates are commercially available, for example example with GENERAL ELECTRIC COMPANY under the LEXAN® brand, TEIJIN under the PANLTTE® brand, BAYER under the brand BAYBLEND®, MOBAY CHEMICAL Corp. under the brand MAKROLON® and DOW CHEMICAL Co. under the brand CALIBRE®.
  • the preferred polycarbonates are homopolycarbonates, in particular in particular the homopolycarbonates of bisphenol-A and tetramethyl-3,5 bisphenol-A (TMBPA).
  • the polycarbonate material contains an amount effective UV absorber.
  • UV absorbers are well-known adjuvants in the field of polymers and are commercially available.
  • UV absorbers mention may be made of benzotriazoles, benzophenones, dihydroxybenzophenones, benzimidazoles and phenyl benzoates.
  • R 3 is an alkyl radical, preferably C 1 -C 13 .
  • R 4 is an alkyl radical, preferably C 1 -C 8 .
  • the proportion of UV absorber in the polycarbonate material generally varies from 0 to 10% by weight relative to the total weight of the material, preferably from 0 to 5%, and more preferably represents 2.5% by weight approximately.
  • the polycarbonate material can include any other adjuvant conventionally used and not detrimental to the optical properties of the material, such as antioxidants, internal or external lubricants, flame retardants and anti-static agents in the proportions usual.
  • any dye or pigment conventionally used for coloring transparent articles made of polymer material y including photochromic dyes and pigments.
  • dyes conventionally used mention may be made of azo dyes and anthraquinone dyes.
  • the azo dyes can be monoazo dyes, for example of formula: where R 8 and R 9 are aryl radicals or heterocycles, preferably heterocycles, or diazo dyes, for example of formula: where R 10 , R 11 and R 12 are aryl radicals or heterocycles, preferably heterocycles.
  • the anthraquinone dyes can be represented by the formula: where R 13 and R 14 represent H, OH, an amine group, an alkoxy group, a fluorocarbon group or an acylamino group.
  • Other dyes can be infrared absorbers or laser dyes.
  • R represents H or an alkyl, preferably C 1 -C 4 .
  • dyes comprising one or more chromophores chosen from one or more complexes of porphyrins that have been modified by metals to form complexes of porphyrin metal.
  • chromophores examples include vanadyl t-butylated phthalocyanine and t-butylated phthalocyanine tin chloride which absorb at a wavelength of 694 nm and which are suitable for protection against a ruby laser.
  • photochromic dyes and pigments that may be mentioned spirooxazines and chromenes.
  • Colorants and photochromic pigments of the type spirooxazine are described, among other things, in patents and applications for US Patents 5,139,707, US-5,114,621, EP-0 245,020, EP-03 88,660 and WO 96/04590.
  • Chromene-type photochromic dyes and pigments are described, among others, in WO patents and patent applications 90/07507, WO 92/09593, WO 93/17071, FR 2 688 782, EP-401958, EP-562915, US-3,567,605 and US-5,066,818.
  • the preferred dyes and pigments are the dyes and pigments azo and anthraquinone.
  • the coloring step of the article is to put the face corresponding to the photodegraded surface layer of the article in polycarbonate material in contact with a coloring agent, for example example in the form of a solution or dispersion of one or more dyes or pigments, in any conventional manner, such as by dipping (dip) in a staining bath or by depositing and centrifuging a coloring solution on the photodegraded side of the article.
  • a coloring agent for example in the form of a solution or dispersion of one or more dyes or pigments
  • bringing the photodegraded face of the article with the coloring agent is carried out by soaking in a bath of coloring.
  • Baths and coloring solutions are conventionally aqueous solutions and dispersions of a dye or pigment or mixtures of dyes and pigments.
  • these baths and solutions also contain a effective amount of a surfactant, in particular an alkyl benzene sulfonate.
  • a surfactant in particular an alkyl benzene sulfonate.
  • the proportion of surfactant in baths or solutions generally vary from 0 to 3%, preferably 0.2% by weight.
  • the temperature of the baths and coloring solutions, during the coloring step is generally between 85 and 100 ° C, in general from 94 to 95 ° C approximately.
  • the articles are subjected to a color stabilization heat treatment, to a temperature preferably above 100 ° C and up to 140 ° C, preferably about 130 ° C, for a time sufficient to fix the coloring, generally 1 hour or more, preferably 2 hours approximately.
  • the primary layers Due to the high impact resistance of the materials polycarbonates, the primary layers have the essential function of serve as a bonding layer promoting adhesion of hard coatings anti-abrasion on the article.
  • composition can be used in the process of the invention primer conventionally used for articles made of polymer material transparent, such as ophthalmic lenses, especially layers of conventional anti-shock primer.
  • thermoplastic polyurethane compositions such as those described in Japanese patents 63-141001 and 63-87223
  • the poly (meth) acrylic primer compositions such as those described in US Pat. No. 5,015,523
  • compositions based on polyurethanes thermosets such as those described in patent EP-0404111
  • compositions based on poly (meth) acrylic latexes and latexes polyurethane such as those described in US Patents 5,316,791 and EP-0680492, WO 98/02376.
  • the preferred primer compositions are the compositions to based on polyurethanes and latex-based compositions, in particular polyurethane latexes.
  • Poly (meth) acrylic latexes are latexes of copolymers mainly constituted by a (meth) acrylate, such as for example the (meth) ethyl or butyl acrylate, or methoxy or ethoxyethyl, with a generally minor proportion of at least one other comonomer, such as for example styrene.
  • the preferred poly (meth) acrylic latexes are acrylate-styrene copolymers.
  • Such acrylate-styrene copolymer latexes are available commercially with ZENECA RESINS under the name NEOCRYL®.
  • Polyurethane latexes are also known and commercially available.
  • polyurethane latexes containing polyester motifs are also marketed by ZENECA RESINS under the name NÉOREZ® and by BAXENDEN CHEMICAL under the name WITCOBOND®.
  • primer compositions can be deposited on the sides of the article by soaking or centrifugation and then dried to temperature of at least 70 ° C and up to 100 ° C, preferably of the order of 90 ° C., for a period of 2 minutes to 2 hours, usually around 15 minutes, to form layers of primer with thicknesses, after firing, of 0.2 to 2.5 ⁇ m, of preferably 0.5 to 1.5 ⁇ m.
  • the method of the invention also includes training on the faces of the article, in particular the photodegraded face of the article, of preferably coated with a layer of primer, a layer of a hard abrasion-resistant coating.
  • compositions for hard abrasion-resistant coating preferred, mention may be made of compositions based on poly (meth) acrylate and compositions based on alkoxysilane hydrolyzate, in particular epoxysilane hydrolyzate, such as those described in the French patent 93,02649 and U.S. Patent 4,211,823.
  • a preferred abrasion-resistant hard coating composition comprises an epoxysilane and dialkyldialcoxysilane hydrolyzate, a colloidal filler, such as colloidal silica, TiO 2 or Sb 2 O 5, and a catalyst, preferably an aluminum chelate, such as aluminum acetylacetonate, the remainder being essentially constituted by solvents conventionally used for the formulation of such compositions.
  • the hydrolyzate used is a hydrolyzate of ⁇ -glycidoxypropyl trimethoxysilane (GLYMO) and dimethyl diethoxysilane (DMDES).
  • GLYMO ⁇ -glycidoxypropyl trimethoxysilane
  • DMDES dimethyl diethoxysilane
  • the primer layer is not necessary for attachment of the abrasion-resistant coating.
  • the thickness of the abrasion-resistant coating is generally between 1 and 10 ⁇ m and more particularly between 2 and 6 ⁇ m.
  • the process of the invention can also include the formation of an anti-reflection layer on the hard abrasion-resistant coating layer.
  • the anti-reflection coating may consist of a mono- or multilayer film, of dielectric materials such as SiO, SiO 2 , Si 3 N 4 , TiO 2 , ZrO 2 , Al 2 O 3 , MgF 2 or Ta 2 O 5 , or mixtures thereof. It thus becomes possible to prevent the appearance of a reflection at the lens-air interface.
  • sol / gel for example from hydrolysates of tetraethoxysilane.
  • the film comprises a single layer
  • its optical thickness must be equal to ⁇ / 4 where ⁇ is a wavelength between 450 and 650 nm.
  • a multilayer film comprising three layers, can use a combination corresponding to optical thicknesses respective ⁇ / 4- ⁇ / 2- ⁇ / 4 or ⁇ / 4- ⁇ / 4- ⁇ / 4.
  • the invention also relates to transparent articles made of polycarbonate material, such as optical glasses and lenses, having two opposite main faces and comprising at least one layer superficial photodegraded from one of the main faces on a thickness of at least 1 ⁇ m, generally from 2 to 20 ⁇ m, and preferably of 2 to 10 ⁇ m throughout the thickness of which a dispersing agent is dispersed coloring.
  • the article has two surface layers photodegraded from the two opposite main faces of the article, each having a thickness of at least 1 ⁇ m, generally 2 to 20 ⁇ m and preferably 2 to 10 ⁇ m, in which the coloring agent is dispersed.
  • the article can be coated on one or on both sides with a primer coat, a hard abrasion-resistant coating and possibly an anti-reflection coating, as described above in conjunction with the method of the invention.
  • a transparent article of material polycarbonate such as a lens 1 is brought by means of a mat 2 under a source of UV radiation.
  • the source of UV radiation by example a UV lamp "D" from the Company FUSION UV SYSTEM operating at 40% of its nominal power, includes a bulb 3 and a reflector 4 focusing the light beam through a frosted quartz 5 on the lens 1 brought by the belt 2.
  • the width of the light beam arriving on the lens is about 1 cm.
  • the photodegradation energy received in 4 seconds by the lens is therefore 16 J / cm 2 for the part of the UV radiation of wavelength ⁇ 320 nm and 5.73 J / cm 2 for the part of the UV radiation> 320 nm.
  • the material polycarbonate of lens 1 is photodegraded, from the upper side of the article, to a depth of at least 1 ⁇ m.
  • the speed of movement of the carpet and therefore the energy received by lens 1 can vary depending on the lamp used and the desired depth of the photodegraded layer, the conditions should always be such as the depth of the layer photodegraded surface of the article made of polycarbonate material at least 1 ⁇ m and better still at least 2 ⁇ m.
  • the conveyor speed is 5 cm / minute at 60 cm / minute, preferably from 10 cm / minute to 30 cm / minute, for obtain the desired irradiation energies.
  • the irradiation must be such that the temperature reached by the irradiated article is lower than the transition temperature glass (Tg) of the polycarbonate material of the article.
  • Tg transition temperature glass
  • the lens is subjected to the treatment of irradiation on its two main faces to form two layers photodegraded surface at least 1 ⁇ m thick each at from the faces of article 1.
  • article 1 is colored, by example by soaking in a coloring bath.
  • the coloring bath is generally at a temperature of 85-100 ° C, and the residence time in the bath can vary from 10 minutes to 1 hour or more, and is typically 30 minutes to 1 hour.
  • compositions of coloring baths are compositions of coloring baths, as well as the color obtained.
  • the above coloring baths are used at a temperature 94 ° C.
  • the article After removal of the article from the coloring bath, the article is generally subjected to salting out treatment of excess staining by immersion in an aqueous polyethylene solution glycol at 55 ° C, then rinsed with deionized water at 55 ° C.
  • the article is preferably subjected to a treatment thermal color stabilization in which the article is heated for 2 hours at 130 ° C.
  • the colored article is pretreated with a sodium hydroxide solution at 50 ° C. for 4 minutes, then immerse the article for 4 minutes in a primer composition, for example a polyurethane latex (Polyester / polyol from BAXENDEN) at 5 ° C. After withdrawal, the primer layer is dried at 80 ° C for 20 minutes and allowed to cool for 15 minutes.
  • a primer composition for example a polyurethane latex (Polyester / polyol from BAXENDEN) at 5 ° C.
  • the primer layer is dried at 80 ° C for 20 minutes and allowed to cool for 15 minutes.
  • the lens is then immersed for 4 minutes in a composition for hard abrasion-resistant coating at 5 ° C.
  • the abrasion-resistant hard coating composition is baked deposited for 3 hours at 100 ° C.
  • An article of colored PC material is thus obtained having a primer layer and a layer of hard abrasion-resistant coating on its two sides.
  • the anti-abrasion coating composition was prepared from the following way:
  • the theoretical dry extract of the composition contains about 13% solid matter from hydrolyzed DMDES.
  • the lenses were deburred and dusted by blowing with compressed air.
  • the lenses were subjected to UV photodegradation treatment above on both sides, then the soaking coloring treatment 20 minutes in the above baths at 94 ° C.
  • the transmission rate ⁇ v was determined (with reference to ISO / CIE standards 10526: 1991 and ISO / CIE 10527: 1991 and the draft ISO / DIS 8980-3 standard from 1997). For all glasses, the transmission rate ⁇ v was 17-30% corresponding to classification 2 as determined in the draft ISO / DIS 8980-3 standard.

Abstract

The invention concerns a method which consists in irradiating at least one face of the article with UV radiation, causing the article to be photodegraded over a thickness of at least 1 mum, and in contacting the irradiated face of the article with a colouring agent so as to diffuse the colouring agent in the entire thickness of the photodegraded surface layer of the article. The invention is useful for optical and ophthalmologic articles.

Description

La présente invention concerne d'une manière générale un procédé de coloration d'un article transparent en polycarbonate, par exemple un article d'optique ou ophtalmique, et en particulier une lentille.The present invention relates generally to a process for coloring a transparent polycarbonate article, by example an optical or ophthalmic article, and in particular a lens.

Il est connu que le polycarbonate (PC) est un matériau difficile à colorer.Polycarbonate (PC) is known to be a difficult material to color.

Les lentilles ophtalmiques en matériau organique classique tel que le matériau obtenu par polymérisation du diallylcarbonate de diéthylèneglycol, sont généralement colorées par trempage dans des bains aqueux de colorants dispersés, les bains étant maintenus à une température de l'ordre de 95°C.Ophthalmic lenses made of conventional organic material such as that the material obtained by polymerization of diallylcarbonate diethylene glycol, are usually colored by soaking in baths aqueous dispersed dyes, the baths being maintained at a temperature of the order of 95 ° C.

Un tel procédé n'est pas directement transposable à la coloration d'articles en polycarbonate, par exemple une lentille en polycarbonate.Such a process cannot be directly transposed to coloring polycarbonate articles, for example a polycarbonate lens.

Diverses techniques ont été proposées pour colorer un article en polycarbonate comme l'application, à la surface de l'article en PC, de solutions de pigments dans un solvant organique capable de partiellement dissoudre ou de gonfler le polycarbonate en surface, de façon à permettre au pigment de pénétrer sous la surface de l'article.Various techniques have been proposed for coloring an article in polycarbonate as the application, on the surface of the PC article, of pigment solutions in an organic solvent capable of partially dissolve or swell the polycarbonate on the surface, so as to allow the pigment to penetrate under the surface of the article.

Ces procédés, agressifs pour la surface de l'article traité, ne conviennent pas dans le cadre d'une application ophtalmique.These processes, aggressive for the surface of the treated article, do not not suitable for ophthalmic application.

Par ailleurs, compte tenu des directives internationales visant à la réduction des solvants organiques, l'utilisation de tels procédés n'est pas souhaitable.Furthermore, taking into account international directives aimed at the reduction of organic solvents, the use of such processes is not not desirable.

Le document US-5 443 597 décrit un procédé de coloration d'un article, tel qu'un élément d'optique, formé d'un copolymère polycarbonate-polyester, qui consiste à soumettre le copolymère à une irradiation UV d'intensité prédéterminée, pendant une durée prédéterminée, puis à soumettre l'article à un traitement de coloration, par exemple par trempage dans une solution aqueuse d'un colorant.Document US Pat. No. 5,443,597 describes a method for coloring a article, such as an optical element, formed from a copolymer polycarbonate-polyester, which consists in subjecting the copolymer to a UV irradiation of predetermined intensity, for a period predetermined, then subjecting the article to a coloring treatment, by example by soaking in an aqueous solution of a dye.

Selon ce document, la présence de chaínons polyesters dans le squelette du copolymère est essentiel car c'est la liaison polyester qui est rompue par l'irradiation et qui permet la pénétration ultérieure du colorant.According to this document, the presence of polyester chains in the backbone of the copolymer is essential because it is the polyester bond which is ruptured by irradiation and which allows subsequent penetration of the dye.

En outre, les profondeurs de pénétration des pigments sont faibles, d'environ 10 à 15 nm. Pour obtenir une pénétration plus importante, le document enseigne que le copolymère doit alors comporter une proportion plus importante de polyester.In addition, the penetration depths of the pigments are weak, about 10 to 15 nm. To get more penetration important, the document teaches that the copolymer must then contain a higher proportion of polyester.

La plupart des matériaux polycarbonates utilisés pour l'optique ophtalmique sont des matériaux à base d'homopolycarbonate.Most polycarbonate materials used for optics Ophthalmic are materials based on homopolycarbonate.

Le document JP 1-118682-A décrit un procédé de coloration de surface d'un film de polycarbonate qui comprend l'irradiation pendant 262 heures de la surface du film par un rayonnement UV puis immersion du film dans une solution de colorant pendant 17 heures.Document JP 1-118682-A describes a process for coloring surface of a polycarbonate film which includes irradiation for 262 hours from the surface of the film by UV radiation then immersion of the film in dye solution for 17 hours.

Il serait donc souhaitable de disposer d'un procédé de coloration simple d'articles en polycarbonate, en particulier en homopolycarbonate, par exemple des articles d'optique et ophtalmiques tels que des lentilles, permettant d'utiliser des colorants classiques en phase aqueuse.It would therefore be desirable to have a coloring process simple of polycarbonate articles, in particular homopolycarbonate, for example optical and ophthalmic articles such as lenses, allowing the use of conventional dyes in the aqueous phase.

En outre, ce procédé, particulièrement destiné à la coloration de lentilles ophtalmiques en PC, en particulier des lentilles pour lunettes, doit non seulement être simple mais permettre une coloration des lentilles à la demande du client.In addition, this process, particularly intended for the coloring of PC ophthalmic lenses, in particular lenses for glasses, must not only be simple but allow a coloring of the lenses at the customer's request.

Il doit permettre de doser l'intensité de coloration : teinte A (claire), teinte B (moyenne), teinte C (foncée).It must allow the intensity of coloring to be determined: shade A (light), shade B (medium), shade C (dark).

Le procédé ne doit pas altérer de façon significative les propriétés essentielles de la lentille telles que la transparence, la résistance aux chocs et aux rayures.The process must not significantly alter the essential properties of the lens such as transparency, impact and scratch resistance.

La coloration obtenue doit être stable dans le temps. The coloration obtained must be stable over time.

On a maintenant trouvé qu'il était possible de provoquer, au moyen d'une irradiation appropriée, une photodégradation du polycarbonate sur une profondeur prédéterminée de l'article en polycarbonate ne comportant pas de motifs polyesters à partir d'une face de l'article, sans altérer notablement les autres propriétés optiques et mécaniques requises, en particulier pour une application en optique ophtalmique.We have now found it possible to provoke, at by means of appropriate irradiation, photodegradation of the polycarbonate over a predetermined depth of the article in polycarbonate not containing polyester motifs from one side of the article, without significantly altering the other optical properties and mechanical requirements, in particular for an optical application ophthalmic.

Un article en PC ainsi traité peut être coloré avec facilité, en particulier au moyen de dispersions et solutions aqueuses de colorants et pigments.An article in PC thus treated can be colored with ease, in particular by means of aqueous dispersions and solutions of dyes and pigments.

Selon l'invention, le procédé de coloration d'un article transparent en matériau polycarbonate ne comportant pas de motifs polyesters, comprend :

  • a) la photodégradation du matériau polycarbonate de l'article transparent par irradiation au moyen d'un rayonnement UV prédéterminé, depuis au moins une première face de l'article, pour réaliser dans l'article au moins une première couche superficielle photodégradée du matériau polycarbonate ayant une épaisseur d'au moins 1 µm, de préférence d'au moins 2 µm; et
  • b) la mise en contact d'au moins ladite première face de l'article avec un agent de coloration pour faire diffuser l'agent de coloration dans une épaisseur d'au moins 1 µm, de préférence d'au moins 2 µm, de la première couche superficielle photodégradée.
    • According to the invention, the process for coloring a transparent article made of polycarbonate material not comprising polyester patterns, comprises:
  • a) the photodegradation of the polycarbonate material of the transparent article by irradiation by means of predetermined UV radiation, from at least one first face of the article, in order to produce in the article at least a first photodegraded surface layer of the polycarbonate material having a thickness of at least 1 µm, preferably at least 2 µm; and
  • b) bringing at least said first face of the article into contact with a coloring agent in order to diffuse the coloring agent in a thickness of at least 1 μm, preferably at least 2 μm, of the first photodegraded surface layer.

    • Bien évidemment, le procédé de l'invention peut aussi comprendre l'irradiation de l'article pour provoquer une photodégradation du matériau polycarbonate depuis deux faces opposées de l'article, (chacune des faces étant alors soumise à la photodégradation) pour former dans l'article deux couches superficielles photodégradées du matériau polycarbonate ayant chacune une épaisseur d'au moins 1 à 2 µm.Obviously, the process of the invention can also understand the irradiation of the item to cause a photodegradation of polycarbonate material from two opposite sides of the article, (each side then being subjected to photodegradation) to form in the article two photodegraded surface layers of the polycarbonate material each having a thickness of at least 1 to 2 µm.

    Dans ce dernier cas, les deux faces de l'article sont alors mises en contact avec l'agent de coloration pour faire diffuser l'agent de coloration dans une épaisseur d'au moins 1 µm, de préférence d'au moins 2 µm, pour chacune des deux couches superficielles photodégradées.In the latter case, the two sides of the article are then placed contact with the coloring agent to spread the coloring agent in a thickness of at least 1 µm, preferably at least 2 µm, for each of the two layers photodegraded surface.

    De préférence, l'épaisseur de la couche superficielle photodégradée ou des couches superficielles photodégradées sera de 2 à 20 µm, et mieux de 2 à 10 µm.Preferably, the thickness of the surface layer photodegraded or photodegraded surface layers will be 2 to 20 µm, and better from 2 to 10 µm.

    L'agent de coloration peut être diffusé dans toute l'épaisseur de la (ou des) couche(s) superficielle(s) photodégradée(s).The coloring agent can be diffused throughout the thickness of the photodegraded surface layer (s).

    Le rayonnement UV de l'étape de photodégradation par irradiation a un spectre de longueur d'onde tel que, lors de l'irradiation, au moins 50%, de préférence au moins 60 %, et mieux encore, au moins 65 % de l'énergie d'irradiation provienne d'une partie du rayonnement de longueur d'onde ≤ 320 nm. De préférence encore, l'énergie d'irradiation de l'article due à la partie du rayonnement UV de longueur d'onde ≤ 320 nm est de 2,4 à 48 J/cm2, mieux de 10 à 30 J/cm2, cependant que l'énergie d'irradiation de l'article due à la partie du rayonnement UV de longueur d'onde > 320 nm est de 0,9 J/cm2 à 15 J/cm2, mieux de 2 J/cm2 à 8 J/cm2. (Comme cela est bien connu, les rayonnements UV ont un spectre de longueur d'onde allant de 200 à 400 nm).The UV radiation from the photodegradation step by irradiation has a wavelength spectrum such that, during irradiation, at least 50%, preferably at least 60%, and better still, at least 65% of l the irradiation energy comes from part of the radiation with a wavelength ≤ 320 nm. More preferably, the irradiation energy of the article due to the part of the UV radiation of wavelength ≤ 320 nm is 2.4 to 48 J / cm 2 , better still 10 to 30 J / cm 2 , however that the irradiation energy of the article due to the part of the UV radiation of wavelength> 320 nm is from 0.9 J / cm 2 to 15 J / cm 2 , better of 2 J / cm 2 to 8 J / cm 2 . (As is well known, UV radiation has a wavelength spectrum ranging from 200 to 400 nm).

    Lors de l'étape de photodégradation, la durée pendant laquelle chaque point de l'une des faces de la lentille est soumis à l'irradiation est inférieure à 10 minutes, de préférence inférieure à 2 minutes et mieux encore inférieure à 30 secondes.During the photodegradation step, the duration for which each point of one of the faces of the lens is subjected to the irradiation is less than 10 minutes, preferably less than 2 minutes and better still less than 30 seconds.

    La durée optimale de l'étape de photodégradation au cours de laquelle les énergies mentionnées plus haut sont reçues par la lentille varie de 0, 1 à 10 secondes, généralement et préférentiellement de 0,4 à 4 secondes.The optimal duration of the photodegradation step during which the energies mentioned above are received by the lens varies from 0.1 to 10 seconds, generally and preferably from 0.4 to 4 seconds.

    On peut montrer la modification de la structure chimique de surface du PC par spectroscopie infrarouge en mode ATR (Attenuated Total Reflectance) à angle de 45°C. Cette technique de surface permet de caractériser la structure de PC dans une profondeur de 1 à 2 µm.We can show the modification of the chemical structure of PC surface by infrared spectroscopy in ATR mode (Attenuated Total Reflectance) at an angle of 45 ° C. This surface technique allows characterize the structure of PC in a depth of 1 to 2 µm.

    On peut voir, par rapport à la surface du PC non dégradé, une augmentation de l'intensité des bandes de stretching (élongation) des groupements OH (alcools, acides, hydroperoxydes) mettant en évidence le processus de photooxydation.We can see, compared to the surface of the PC not degraded, a increase in the intensity of the stretching bands OH groups (alcohols, acids, hydroperoxides) highlighting the photooxidation process.

    Les rayonnements UV convenant pour le procédé de l'invention peuvent être obtenus, par exemple en utilisant une lampe UV "H" de la Société FUSION UV SYSTEM à 50% de sa puissance nominale ou une lampe UV "D" de cette même société à 40% de sa puissance nominale.UV radiation suitable for the process of the invention can be obtained, for example using a UV lamp "H" from the Company FUSION UV SYSTEM at 50% of its nominal power or one UV lamp "D" from the same company at 40% of its nominal power.

    L'article "Photovieillissement : évaluation des sources lumineuses", Agnès RIVATON, Jean-Luc GARDETTE et Jacques LEMAIRE, Caoutchoucs et Plastiques n° 651 - Mai 1985, pages 81 à 85, montre que le photovieillissement du polycarbonate de bisphénol-A possède une double photochimie, à savoir une photochimie "intrinsèque" (attaque de surface) et une photochimie "induite" associée à l'excitation des défauts ou impuretés (attaque en profondeur).The article "Photoaging: assessment of sources luminous ", Agnès RIVATON, Jean-Luc GARDETTE and Jacques LEMAIRE, Rubbers and Plastics n ° 651 - May 1985, pages 81 to 85, shows that photoaging of bisphenol-A polycarbonate has a double photochemistry, namely an "intrinsic" photochemistry (surface attack) and an "induced" photochemistry associated with excitement faults or impurities (deep attack).

    Sans vouloir être lié par une théorie, on pense que pour former les couches superficielles photodégradées selon l'invention, l'irradiation UV de l'article en polycarbonate doit être telle que le photovieillissement procède essentiellement selon une photochimie "intrinsèque", c'est-à-dire une attaque de surface. Ainsi, on peut obtenir un article en matériau polycarbonate ayant une couche superficielle photodégradée améliorant l'aptitude à la coloration de l'article sans nuire aux autres propriétés optiques et mécaniques du matériau polycarbonate.Without wanting to be bound by a theory, we think that to form the photodegraded surface layers according to the invention, the irradiation UV of the polycarbonate article should be such that photoaging essentially proceeds according to an "intrinsic" photochemistry, that is to say a surface attack. So, we can get an article in material polycarbonate having a photodegraded surface layer improving the ability to color the article without harming other properties optical and mechanical of the polycarbonate material.

    Les polycarbonates convenant pour la présente invention sont tous les polycarbonates ne comportant pas de motifs polyesters.The polycarbonates suitable for the present invention are all polycarbonates not containing polyester units.

    On entend par polycarbonate dans la présente invention, aussi bien les homopolycarbonates que les copolycarbonates et copolycarbonates séquencés, étant entendu que les copolycarbonates comportant des motifs polyesters sont exclus.Polycarbonate is understood in the present invention, also homopolycarbonates as well as copolycarbonates and block copolycarbonates, it being understood that the copolycarbonates with polyester motifs are excluded.

    Ces polycarbonates sont disponibles dans le commerce, par exemple auprès des Sociétés GENERAL ELECTRIC COMPANY sous la marque LEXAN®, TEIJIN sous la marque PANLTTE®, BAYER sous la marque BAYBLEND®, MOBAY CHEMICAL Corp. sous la marque MAKROLON® et DOW CHEMICAL Co. sous la marque CALIBRE®.These polycarbonates are commercially available, for example example with GENERAL ELECTRIC COMPANY under the LEXAN® brand, TEIJIN under the PANLTTE® brand, BAYER under the brand BAYBLEND®, MOBAY CHEMICAL Corp. under the brand MAKROLON® and DOW CHEMICAL Co. under the brand CALIBRE®.

    Les polycarbonates préférés sont les homopolycarbonates, en particulier les homopolycarbonates de bisphénol-A et de tétraméthyl-3,5 bisphénol-A (TMBPA).The preferred polycarbonates are homopolycarbonates, in particular in particular the homopolycarbonates of bisphenol-A and tetramethyl-3,5 bisphenol-A (TMBPA).

    De préférence, le matériau polycarbonate contient une quantité effective d'un absorbeur UV.Preferably, the polycarbonate material contains an amount effective UV absorber.

    Les absorbeurs UV sont des adjuvants bien connus dans le domaine des polymères et sont disponibles dans le commerce.UV absorbers are well-known adjuvants in the field of polymers and are commercially available.

    Parmi ces absorbeurs UV on peut citer les benzotriazoles, les benzophénones, les dihydroxybenzophénones, les benzimidazoles et les phényl benzoates.Among these UV absorbers, mention may be made of benzotriazoles, benzophenones, dihydroxybenzophenones, benzimidazoles and phenyl benzoates.

    Parmi les benzotriazoles, on peut citer les benzotriazoles de formule :

    Figure 00060001
    où

  • R1 représente H ou un radical alkyle, de préférence en C1-C6,
  • R2 représente H ou un radical alkyle, de préférence en C1-C8, et
  • X représente H ou Cl.
    • Among the benzotriazoles, mention may be made of the benzotriazoles of formula:
    Figure 00060001
    or
  • R 1 represents H or an alkyl radical, preferably C 1 -C 6 ,
  • R 2 represents H or an alkyl radical, preferably C 1 -C 8 , and
  • X represents H or Cl.

    • Parmi les benzophénones, on peut citer les composés de formule :

    Figure 00070001
       où R3 est un radical alkyle, de préférence en C1-C13.Among the benzophenones, mention may be made of the compounds of formula:
    Figure 00070001
    where R 3 is an alkyl radical, preferably C 1 -C 13 .

    Parmi les dihydroxybenzophénones, on peut citer les composés de formule :

    Figure 00070002
       où R4 est un radical alkyle, de préférence en C1-C8.Among the dihydroxybenzophenones, mention may be made of the compounds of formula:
    Figure 00070002
    where R 4 is an alkyl radical, preferably C 1 -C 8 .

    Parmi les phényl benzoates, on peut citer les composés de formule :

    Figure 00080001
    où

  • R5 représente H ou un radical alkyle, de préférence en C1-C4, et
  • R6 et R7 représentent H ou OH.
    • Among the phenyl benzoates, mention may be made of the compounds of formula:
    Figure 00080001
    or
  • R 5 represents H or an alkyl radical, preferably C 1 -C 4 , and
  • R 6 and R 7 represent H or OH.

    • La proportion d'absorbeur UV dans le matériau polycarbonate varie en général de 0 à 10% en poids par rapport au poids total du matériau, de préférence de 0 à 5%, et mieux représente 2,5% en poids environ.The proportion of UV absorber in the polycarbonate material generally varies from 0 to 10% by weight relative to the total weight of the material, preferably from 0 to 5%, and more preferably represents 2.5% by weight approximately.

    Le matériau polycarbonate peut comporter tout autre adjuvant classiquement utilisé et ne nuisant pas aux propriétés optiques du matériau, tel que des antioxydants, des lubrifiants internes ou externes, des agents ignifugeants et des agents anti-statiques dans les proportions usuelles.The polycarbonate material can include any other adjuvant conventionally used and not detrimental to the optical properties of the material, such as antioxidants, internal or external lubricants, flame retardants and anti-static agents in the proportions usual.

    On peut utiliser dans l'étape de coloration de l'article, selon le procédé de l'invention, tout colorant ou pigment classiquement utilisé pour la coloration des articles transparents en matériau polymère y compris des colorants et pigments photochromiques.It can be used in the coloring step of the article, depending on the process of the invention, any dye or pigment conventionally used for coloring transparent articles made of polymer material y including photochromic dyes and pigments.

    On peut aussi, à ce stade, faire également diffuser un absorbeur UV.You can also, at this stage, also distribute an absorber UV.

    Parmi les colorants classiquement utilisés, on peut citer les colorants azoïques et les colorants anthraquinoniques.Among the dyes conventionally used, mention may be made of azo dyes and anthraquinone dyes.

    Les colorants azoïques peuvent être des colorants monoazoïques, par exemple de formule :

    Figure 00080002
    où R8 et R9 sont des radicaux aryles ou des hétérocycles, de préférence des hétérocycles, ou des colorants diazoïques, par exemple de formule :
    Figure 00090001
       où R10, R11 et R12 sont des radicaux aryles ou des hétérocycles, de préférence des hétérocycles.The azo dyes can be monoazo dyes, for example of formula:
    Figure 00080002
    where R 8 and R 9 are aryl radicals or heterocycles, preferably heterocycles, or diazo dyes, for example of formula:
    Figure 00090001
    where R 10 , R 11 and R 12 are aryl radicals or heterocycles, preferably heterocycles.

    Les colorants anthraquinoniques peuvent être représentés par la formule :

    Figure 00090002
       où R13 et R14 représentent H, OH, un groupe amine, un groupe alcoxy, un groupe fluorocarboné ou un groupe acylamino.The anthraquinone dyes can be represented by the formula:
    Figure 00090002
    where R 13 and R 14 represent H, OH, an amine group, an alkoxy group, a fluorocarbon group or an acylamino group.

    D'autres colorants peuvent être des absorbeurs infrarouges ou des colorants lasers.Other dyes can be infrared absorbers or laser dyes.

    Parmi les absorbeurs infrarouges, on peut citer les composés suivants :

    Figure 00100001
       dans lesquels R représente H ou un alkyle, de préférence en C1-C4.
    Figure 00110001
    Figure 00110002
    Figure 00110003
    Among the infrared absorbers, the following compounds may be mentioned:
    Figure 00100001
    in which R represents H or an alkyl, preferably C 1 -C 4 .
    Figure 00110001
    Figure 00110002
    Figure 00110003

    Parmi les colorants laser, on peut citer les colorants comportant un ou plusieurs chromophores choisis parmi un ou plusieurs complexes de porphyrine qui ont été modifiés par des métaux pour former des complexes de métal porphyrine.Among the laser dyes, mention may be made of dyes comprising one or more chromophores chosen from one or more complexes of porphyrins that have been modified by metals to form complexes of porphyrin metal.

    Des exemples de chromophores convenables sont la vanadyl phtalocyanine t-butylée et le chlorure d'étain de la phtalocyanine t-butylée qui absorbent à une longueur d'onde de 694 nm et qui conviennent pour la protection vis-à-vis d'un laser à rubis.Examples of suitable chromophores are vanadyl t-butylated phthalocyanine and t-butylated phthalocyanine tin chloride which absorb at a wavelength of 694 nm and which are suitable for protection against a ruby laser.

    Parmi les colorants et pigments photochromiques, on peut citer les spirooxazines et les chromènes.Among the photochromic dyes and pigments that may be mentioned spirooxazines and chromenes.

    Des colorants et pigments photochromiques du type spirooxazine sont décrits, entre autres, dans les brevets et demandes de brevets US-5 139 707, US-5 114 621, EP-0 245 020, EP-03 88 660 et WO 96/04590.Colorants and photochromic pigments of the type spirooxazine are described, among other things, in patents and applications for US Patents 5,139,707, US-5,114,621, EP-0 245,020, EP-03 88,660 and WO 96/04590.

    Des colorants et pigments photochromiques du type chromène sont décrits, entre autres, dans les brevets et demandes de brevets WO 90/07507, WO 92/09593, WO 93/17071, FR 2 688 782, EP-401958, EP-562915, US-3 567 605 et US-5 066 818.Chromene-type photochromic dyes and pigments are described, among others, in WO patents and patent applications 90/07507, WO 92/09593, WO 93/17071, FR 2 688 782, EP-401958, EP-562915, US-3,567,605 and US-5,066,818.

    Les colorants et pigments préférés sont les colorants et pigments azoïques et anthraquinoniques.The preferred dyes and pigments are the dyes and pigments azo and anthraquinone.

    L'étape de coloration de l'article consiste à mettre la face correspondant à la couche superficielle photodégradée de l'article en matériau polycarbonate en contact avec un agent de coloration, par exemple sous forme d'une solution ou dispersion d'un ou plusieurs colorants ou pigments, de toute manière classique, telle que par trempage (dip) dans un bain de coloration ou par dépôt et centrifugation d'une solution de coloration sur la face photodégradée de l'article.The coloring step of the article is to put the face corresponding to the photodegraded surface layer of the article in polycarbonate material in contact with a coloring agent, for example example in the form of a solution or dispersion of one or more dyes or pigments, in any conventional manner, such as by dipping (dip) in a staining bath or by depositing and centrifuging a coloring solution on the photodegraded side of the article.

    De préférence, la mise en contact de la face photodégradée de l'article avec l'agent de coloration s'effectue par trempage dans un bain de coloration.Preferably, bringing the photodegraded face of the article with the coloring agent is carried out by soaking in a bath of coloring.

    Les bains et solutions de coloration sont classiquement des solutions et dispersions aqueuses d'un colorant ou d'un pigment ou de mélanges de colorants et pigments.Baths and coloring solutions are conventionally aqueous solutions and dispersions of a dye or pigment or mixtures of dyes and pigments.

    De préférence, ces bains et solutions contiennent également une quantité effective d'un agent tensio-actif, en particulier un alkyl benzène sulfonate. La proportion d'agent tensio-actif dans les bains ou les solutions varie généralement de 0 à 3%, préférentiellement 0,2% en poids.Preferably, these baths and solutions also contain a effective amount of a surfactant, in particular an alkyl benzene sulfonate. The proportion of surfactant in baths or solutions generally vary from 0 to 3%, preferably 0.2% by weight.

    La température des bains et solutions de coloration, lors de l'étape de coloration, est généralement comprise entre 85 et 100°C, en général de 94 à 95°C environ.The temperature of the baths and coloring solutions, during the coloring step is generally between 85 and 100 ° C, in general from 94 to 95 ° C approximately.

    De préférence, après le traitement de coloration, les articles sont soumis à un traitement thermique de stabilisation de la coloration, à une température de préférence supérieure à 100°C et pouvant atteindre jusqu'à 140°C, de préférence de 130°C environ, pendant une durée suffisante pour fixer la coloration, généralement de 1 heure ou plus, de préférence de 2 heures environ.Preferably, after the coloring treatment, the articles are subjected to a color stabilization heat treatment, to a temperature preferably above 100 ° C and up to 140 ° C, preferably about 130 ° C, for a time sufficient to fix the coloring, generally 1 hour or more, preferably 2 hours approximately.

    Après le traitement de coloration et l'éventuel traitement thermique de stabilisation, on peut dans le procédé de l'invention procéder aux dépôts classiques sur les faces de l'article de couches de primaire, revêtement dur anti-abrasion et revêtement anti-reflets.After the coloring treatment and any treatment thermal stabilization, it is possible in the process of the invention to proceed with conventional deposits on the faces of the article with primer layers, hard abrasion-resistant coating and anti-reflective coating.

    Etant donné la résistance aux chocs élevée des matériaux polycarbonates, les couches de primaire ont pour fonction essentielle de servir de couche d'accrochage favorisant l'adhésion des revêtements durs anti-abrasion sur l'article.Due to the high impact resistance of the materials polycarbonates, the primary layers have the essential function of serve as a bonding layer promoting adhesion of hard coatings anti-abrasion on the article.

    On a également trouvé que le dépôt de telles couches de primaire sur les faces photodégradées des articles supprimait les défauts de surface et perte d'adhérence éventuels dus à la photodégradation ou autres.It has also been found that the deposition of such primer layers on the photodegraded faces of the articles eliminated surface defects and possible loss of adhesion due to photodegradation or others.

    On peut utiliser dans le procédé de l'invention toute composition de primaire classiquement utilisée pour les articles en matériau polymère transparent, tels que des lentilles ophtalmiques, en particulier les couches de primaire anti-chocs classiques.Any composition can be used in the process of the invention primer conventionally used for articles made of polymer material transparent, such as ophthalmic lenses, especially layers of conventional anti-shock primer.

    Parmi les compositions de primaires préférés, on peut citer les compositions à base de polyuréthanne thermoplastiques, telles celles décrites dans les brevets japonais 63-141001 et 63-87223, les compositions de primaires poly(méth)acryliques, telles celles décrites dans le brevet US-5 015 523, les compositions à base de polyuréthannes thermodurcissables, telles celles décrites dans le brevet EP-0404111 et les compositions à base de latex poly(méth)acryliques et latex de polyuréthanne, telles celles décrites dans les brevets US-5 316 791 et EP-0680492, WO 98/02376.Among the preferred primary compositions, mention may be made of thermoplastic polyurethane compositions, such as those described in Japanese patents 63-141001 and 63-87223, the poly (meth) acrylic primer compositions, such as those described in US Pat. No. 5,015,523, compositions based on polyurethanes thermosets, such as those described in patent EP-0404111 and compositions based on poly (meth) acrylic latexes and latexes polyurethane, such as those described in US Patents 5,316,791 and EP-0680492, WO 98/02376.

    Les compositions de primaire préférées sont les compositions à base de polyuréthannes et les compositions à base de latex, en particulier les latex de polyuréthannes.The preferred primer compositions are the compositions to based on polyurethanes and latex-based compositions, in particular polyurethane latexes.

    Les latex poly(méth)acryliques sont des latex de copolymères constitués principalement par un (méth)acrylate, tel que par exemple le (méth)acrylate d'éthyle ou de butyle, ou de méthoxy ou éthoxyéthyle, avec une proportion généralement mineure d'au moins un autre comonomère, tel que par exemple du styrène.Poly (meth) acrylic latexes are latexes of copolymers mainly constituted by a (meth) acrylate, such as for example the (meth) ethyl or butyl acrylate, or methoxy or ethoxyethyl, with a generally minor proportion of at least one other comonomer, such as for example styrene.

    Les latex poly(méth)acryliques préférés sont les latex de copolymères acrylate-styrène.The preferred poly (meth) acrylic latexes are acrylate-styrene copolymers.

    De tels latex de copolymères acrylate-styrène sont disponibles commercialement auprès de la Société ZENECA RESINS sous la dénomination NÉOCRYL®.Such acrylate-styrene copolymer latexes are available commercially with ZENECA RESINS under the name NEOCRYL®.

    Les latex de polyuréthannes sont également connus et disponibles dans le commerce.Polyurethane latexes are also known and commercially available.

    A titre d'exemple, on peut citer les latex de polyuréthannes contenant des motifs polyesters. De tels latex sont également commercialisés par la Société ZENECA RESINS sous la dénomination NÉOREZ® et par la Société BAXENDEN CHEMICAL sous la dénomination WITCOBOND®.By way of example, mention may be made of polyurethane latexes containing polyester motifs. Such latexes are also marketed by ZENECA RESINS under the name NÉOREZ® and by BAXENDEN CHEMICAL under the name WITCOBOND®.

    On peut également utiliser pour les primaires des mélanges de ces latex, en particulier de latex polyuréthanne et de latex poly(méth)acrylique.Mixtures of these latexes, in particular polyurethane latex and latex poly (meth) acrylic acid.

    Ces compositions de primaire peuvent être déposées sur les faces de l'article par trempage ou centrifugation puis séchées à une température d'au moins 70°C et pouvant aller jusqu'à 100°C, de préférence de l'ordre de 90°C, pendant une durée de 2 minutes à 2 heures, généralement de l'ordre de 15 minutes, pour former des couches de primaire ayant des épaisseurs, après cuisson, de 0,2 à 2,5 µm, de préférence 0,5 à 1,5 µm.These primer compositions can be deposited on the sides of the article by soaking or centrifugation and then dried to temperature of at least 70 ° C and up to 100 ° C, preferably of the order of 90 ° C., for a period of 2 minutes to 2 hours, usually around 15 minutes, to form layers of primer with thicknesses, after firing, of 0.2 to 2.5 µm, of preferably 0.5 to 1.5 µm.

    Le procédé de l'invention comprend également la formation sur les faces de l'article, en particulier la face photodégradée de l'article, de préférence revêtue d'une couche de primaire, d'une couche d'un revêtement dur anti-abrasion.The method of the invention also includes training on the faces of the article, in particular the photodegraded face of the article, of preferably coated with a layer of primer, a layer of a hard abrasion-resistant coating.

    On peut utiliser pour former cette couche de revêtement dur anti-abrasion, toute composition classiquement utilisée à cette fin, en particulier dans le domaine de l'optique ophtalmique.We can use to form this layer of hard abrasion-resistant coating, any composition conventionally used for this purpose, in particularly in the field of ophthalmic optics.

    Parmi les compositions pour revêtement dur anti-abrasion préférées, on peut citer les compositions à base de poly(méth)acrylate et les compositions à base d'hydrolysat d'alcoxysilane, en particulier d'hydrolysat d'époxysilane, telles celles décrites dans le brevet français 93 02649 et le brevet US-4 211 823.Among the compositions for hard abrasion-resistant coating preferred, mention may be made of compositions based on poly (meth) acrylate and compositions based on alkoxysilane hydrolyzate, in particular epoxysilane hydrolyzate, such as those described in the French patent 93,02649 and U.S. Patent 4,211,823.

    Une composition pour revêtement dur anti-abrasion préférée comprend un hydrolysat d'époxysilane et de dialkyldialcoxysilane, une charge colloïdale, telle que de la silice colloïdale, TiO2 ou Sb2O5 et un catalyseur, de préférence un chélate d'aluminium, tel que l'acétylacétonate d'aluminium, le reste étant essentiellement constitué par des solvants classiquement utilisés pour la formulation de telles compositions.A preferred abrasion-resistant hard coating composition comprises an epoxysilane and dialkyldialcoxysilane hydrolyzate, a colloidal filler, such as colloidal silica, TiO 2 or Sb 2 O 5, and a catalyst, preferably an aluminum chelate, such as aluminum acetylacetonate, the remainder being essentially constituted by solvents conventionally used for the formulation of such compositions.

    Préférentiellement, l'hydrolysat utilisé est un hydrolysat de γ-glycidoxypropyl triméthoxysilane (GLYMO) et de diméthyl diéthoxysilane (DMDES).Preferably, the hydrolyzate used is a hydrolyzate of γ-glycidoxypropyl trimethoxysilane (GLYMO) and dimethyl diethoxysilane (DMDES).

    A titre d'exemple, on peut citer une composition obtenue par hydrolyse d'un mélange en poids de 224 parties de GLYMO et 120 parties de DMDES, à laquelle on a ajouté 718 parties en poids de silice colloïdale à 30% dans le méthanol, 15 parties d'acétylacétonate d'aluminium et 44 parties d'éthylcellosolve.By way of example, there may be mentioned a composition obtained by hydrolysis of a mixture by weight of 224 parts of GLYMO and 120 parts DMDES, to which was added 718 parts by weight of colloidal silica 30% in methanol, 15 parts of aluminum acetylacetonate and 44 parts of ethylcellosolve.

    Dans le cas d'une composition dure anti-abrasion à base de poly(méth)acrylate, la couche de primaire n'est pas nécessaire pour l'accrochage du revêtement anti-abrasion.In the case of a hard anti-abrasion composition based on poly (meth) acrylate, the primer layer is not necessary for attachment of the abrasion-resistant coating.

    L'épaisseur du revêtement anti-abrasion est généralement comprise entre 1 et 10 µm et plus particulièrement entre 2 et 6 µm.The thickness of the abrasion-resistant coating is generally between 1 and 10 µm and more particularly between 2 and 6 µm.

    Par contre, une telle couche de primaire s'avère pratiquement nécessaire dans le cas d'un revêtement anti-abrasion à base d'hydrolysat d'époxysilane.On the other hand, such a primer layer proves practically necessary in the case of an abrasion-resistant coating based on hydrolyzate epoxysilane.

    Le procédé de l'invention peut également comporter la formation d'une couche anti-reflets sur la couche de revêtement dur anti-abrasion.The process of the invention can also include the formation of an anti-reflection layer on the hard abrasion-resistant coating layer.

    A titre d'exemple, le revêtement anti-reflets peut être constitué d'un film mono- ou multicouche, de matériaux diélectriques tels que SiO, SiO2, Si3N4, TiO2, ZrO2, Al2O3, MgF2 ou Ta2O5, ou leurs mélanges. Il devient ainsi possible d'empêcher l'apparition d'une réflexion à l'interface lentille-air.For example, the anti-reflection coating may consist of a mono- or multilayer film, of dielectric materials such as SiO, SiO 2 , Si 3 N 4 , TiO 2 , ZrO 2 , Al 2 O 3 , MgF 2 or Ta 2 O 5 , or mixtures thereof. It thus becomes possible to prevent the appearance of a reflection at the lens-air interface.

    Ce revêtement anti-reflets est appliqué généralement par dépôt sous vide selon l'une des techniques suivantes :

  • 1/ Par évaporation, éventuellement assistée par faisceau ionique.
  • 2/ Par pulvérisation par faisceau d'ions.
  • 3/ Par pulvérisation cathodique.
  • 4/ Par dépôt chimique en phase vapeur assisté par plasma.
    • This anti-reflection coating is generally applied by vacuum deposition according to one of the following techniques:
  • 1 / By evaporation, possibly assisted by ion beam.
  • 2 / By ion beam spraying.
  • 3 / By sputtering.
  • 4 / By chemical vapor deposition assisted by plasma.

    • Outre le dépôt sous vide, on peut aussi envisager un dépôt d'une couche minérale par voie sol/gel, (par exemple à partir d'hydrolysats de tétraéthoxysilane).In addition to vacuum deposition, one can also consider depositing a mineral layer by sol / gel, (for example from hydrolysates of tetraethoxysilane).

    Dans le cas où la pellicule comprend une seule couche, son épaisseur optique doit être égale à λ/4 où λ est une longueur d'onde comprise entre 450 et 650 nm.In the case where the film comprises a single layer, its optical thickness must be equal to λ / 4 where λ is a wavelength between 450 and 650 nm.

    Dans le cas d'un film multicouche comportant trois couches, on peut utiliser une combinaison correspondant à des épaisseurs optiques respectives λ/4-λ/2-λ/4 ou λ/4-λ/4-λ/4.In the case of a multilayer film comprising three layers, can use a combination corresponding to optical thicknesses respective λ / 4-λ / 2-λ / 4 or λ / 4-λ / 4-λ / 4.

    On peut en outre utiliser un film équivalent formé par plus de couches, à la place de l'une quelconque des couches faisant partie des trois couches précitées.It is also possible to use an equivalent film formed by more than layers, instead of any of the three layers aforementioned layers.

    L'invention concerne également des articles transparents en matériau polycarbonate, tels que des verres optiques et des lentilles, ayant deux faces principales opposées et comprenant au moins une couche superficielle photodégradée depuis une des faces principales sur une épaisseur d'au moins 1 µm, généralement de 2 à 20 µm, et de préférence de 2 à 10 µm dans la totalité de l'épaisseur de laquelle est dispersé un agent de coloration.The invention also relates to transparent articles made of polycarbonate material, such as optical glasses and lenses, having two opposite main faces and comprising at least one layer superficial photodegraded from one of the main faces on a thickness of at least 1 µm, generally from 2 to 20 µm, and preferably of 2 to 10 µm throughout the thickness of which a dispersing agent is dispersed coloring.

    De préférence, l'article comporte deux couches superficielles photodégradées depuis les deux faces principales opposées de l'article, ayant chacune une épaisseur d'au moins 1 µm, généralement 2 à 20 µm et de préférence 2 à 10 µm, dans lesquelles est dispersé l'agent de coloration.Preferably, the article has two surface layers photodegraded from the two opposite main faces of the article, each having a thickness of at least 1 µm, generally 2 to 20 µm and preferably 2 to 10 μm, in which the coloring agent is dispersed.

    L'article peut être revêtu sur une ou sur ses deux faces d'une couche de primaire, d'un revêtement dur anti-abrasion et éventuellement d'un revêtement anti-reflets, comme décrit précédemment en liaison avec le procédé de l'invention.The article can be coated on one or on both sides with a primer coat, a hard abrasion-resistant coating and possibly an anti-reflection coating, as described above in conjunction with the method of the invention.

    La suite de la description se réfère aux figures annexées, qui représentent respectivement :

  • Figure 1 - une vue de face schématique d'un dispositif de mise en oeuvre de l'étape d'irradiation d'un article transparent, tel qu'une lentille, en matériau polycarbonate, selon le procédé de l'invention; et
  • Figure 2 - un graphe du spectre de rayonnement de la source de lumière UV du dispositif de la figure 1.
    • The following description refers to the appended figures, which respectively represent:
  • Figure 1 - a schematic front view of a device for implementing the step of irradiating a transparent article, such as a lens, made of polycarbonate material, according to the method of the invention; and
  • Figure 2 - a graph of the radiation spectrum of the UV light source of the device in Figure 1.

    • En se référant à la figure 1, un article transparent en matériau polycarbonate tel qu'une lentille 1, est amené au moyen d'un tapis 2 sous une source de rayonnement UV. La source de rayonnement UV, par exemple une lampe UV "D" de la Société FUSION UV SYSTEM fonctionnant à 40% de sa puissance nominale, comprend un bulbe 3 et un réflecteur 4 focalisant le faisceau lumineux à travers un quartz dépoli 5 sur la lentille 1 amenée par le tapis 2.Referring to Figure 1, a transparent article of material polycarbonate such as a lens 1, is brought by means of a mat 2 under a source of UV radiation. The source of UV radiation, by example a UV lamp "D" from the Company FUSION UV SYSTEM operating at 40% of its nominal power, includes a bulb 3 and a reflector 4 focusing the light beam through a frosted quartz 5 on the lens 1 brought by the belt 2.

    Le spectre du rayonnement UV émis par la lampe UV "D" fonctionnant à 40% de sa puissance nominale est représenté à la figure 2.The spectrum of UV radiation emitted by the UV lamp "D" operating at 40% of its nominal power is shown in Figure 2.

    Avec une vitesse de défilement du tapis de 15 cm/minute, le bulbe 3 de la lampe située à 10 cm au-dessus du tapis et la lampe UV "D" fonctionnant à 40% de sa puissance nominale, la largeur du faisceau lumineux arrivant sur la lentille est de 1 cm environ. L'énergie de photodégradation reçue en 4 secondes par la lentille est donc de 16 J/cm2 pour la partie du rayonnement UV de longueur d'onde ≤ 320 nm et de 5,73 J/cm2 pour la partie du rayonnement UV > 320 nm.With a running speed of the carpet of 15 cm / minute, the bulb 3 of the lamp located 10 cm above the carpet and the UV lamp "D" operating at 40% of its nominal power, the width of the light beam arriving on the lens is about 1 cm. The photodegradation energy received in 4 seconds by the lens is therefore 16 J / cm 2 for the part of the UV radiation of wavelength ≤ 320 nm and 5.73 J / cm 2 for the part of the UV radiation> 320 nm.

    En procédant comme indiqué ci-dessus, le matériau polycarbonate de la lentille 1 est photodégradé, depuis la face supérieure de l'article, sur une profondeur d'au moins 1 µm.By proceeding as indicated above, the material polycarbonate of lens 1 is photodegraded, from the upper side of the article, to a depth of at least 1 µm.

    Bien évidemment, la vitesse de défilement du tapis et donc l'énergie reçue par la lentille 1 peuvent varier en fonction de la lampe utilisée et de la profondeur voulue de la couche photodégradée, les conditions devant toujours être telles que la profondeur de la couche superficielle photodégradée de l'article en matériau polycarbonate soit d'au moins 1 µm et mieux d'au moins 2 µm.Obviously, the speed of movement of the carpet and therefore the energy received by lens 1 can vary depending on the lamp used and the desired depth of the photodegraded layer, the conditions should always be such as the depth of the layer photodegraded surface of the article made of polycarbonate material at least 1 µm and better still at least 2 µm.

    En général, la vitesse de défilement du tapis est de 5 cm/minute à 60 cm/minute, de préférence de 10 cm/minute à 30 cm/minute, pour obtenir les énergies d'irradiation voulues.In general, the conveyor speed is 5 cm / minute at 60 cm / minute, preferably from 10 cm / minute to 30 cm / minute, for obtain the desired irradiation energies.

    Dans tous les cas, l'irradiation doit être telle que la température atteinte par l'article irradié soit inférieure à la température de transition vitreuse (Tg) du matériau polycarbonate de l'article.In all cases, the irradiation must be such that the temperature reached by the irradiated article is lower than the transition temperature glass (Tg) of the polycarbonate material of the article.

    De préférence encore, la lentille est soumise au traitement d'irradiation sur ses deux faces principales pour former deux couches superficielles photodégradées d'au moins 1 µm d'épaisseur chacune à partir des faces de l'article 1. More preferably, the lens is subjected to the treatment of irradiation on its two main faces to form two layers photodegraded surface at least 1 µm thick each at from the faces of article 1.

    Après le traitement d'irradiation, l'article 1 est coloré, par exemple par trempage dans un bain de coloration. Le bain de coloration est généralement à une température de 85-100°C, et le temps de séjour dans le bain peut varier de 10 minutes à 1 heure ou plus, et est en général de 30 minutes à 1 heure.After the irradiation treatment, article 1 is colored, by example by soaking in a coloring bath. The coloring bath is generally at a temperature of 85-100 ° C, and the residence time in the bath can vary from 10 minutes to 1 hour or more, and is typically 30 minutes to 1 hour.

    A titre d'exemple, on indique ci-après des compositions de bains de coloration, ainsi que la couleur obtenue. Bain 1 Couleur vert Bain 2 Couleur gris Bain 3 Couleur marron Eau 1 l 1 l 1 l AKBS 2 ml 2 ml 2 ml Bleu TERATOP® GLF 1,25 g 3,95 g 0,95 g Jaune TERATOP® GNL 9,5 g 8 g 12 g Rouge TERATOP® 3G 0,1 g 0,75 g 0,33 g AKBS : Alkyl benzène sulfonate. (Ces bains sont obtenus en mélangeant les différents ingrédients dans l'eau à 60°C).By way of example, the following are compositions of coloring baths, as well as the color obtained. Bath 1 Green color Bath 2 Gray color Bath 3 Brown color Water 1 l 1 l 1 l AKBS 2 ml 2 ml 2 ml TERATOP® GLF Blue 1.25 g 3.95 g 0.95 g TERATOP® LNG yellow 9.5 g 8 g 12 g TERATOP® 3G red 0.1g 0.75 g 0.33 g AKBS: Alkyl benzene sulfonate. (These baths are obtained by mixing the different ingredients in water at 60 ° C).

    Les bains de coloration ci-dessus sont utilisés à une température de 94°C.The above coloring baths are used at a temperature 94 ° C.

    Après retrait de l'article du bain de coloration, l'article est généralement soumis à un traitement de relargage de l'excès d'agent de coloration par immersion dans une solution aqueuse de polyéthylène glycol à 55°C, puis rincée avec de l'eau désionisée à 55°C.After removal of the article from the coloring bath, the article is generally subjected to salting out treatment of excess staining by immersion in an aqueous polyethylene solution glycol at 55 ° C, then rinsed with deionized water at 55 ° C.

    A ce stade, l'article est de préférence soumis à un traitement thermique de stabilisation de la coloration dans lequel l'article est chauffé pendant 2 heures à 130°C.At this stage, the article is preferably subjected to a treatment thermal color stabilization in which the article is heated for 2 hours at 130 ° C.

    On va maintenant décrire un exemple de réalisation sur l'article coloré obtenu, d'un revêtement dur anti-abrasion.We will now describe an example of an embodiment on the article colored obtained, of a hard abrasion-resistant coating.

    L'article coloré est prétraité avec une solution de soude à 50°C pendant 4 minutes, puis on immerge l'article pendant 4 minutes dans une composition de primaire, par exemple un latex de polyuréthanne (Polyester/polyol de la Société BAXENDEN) à 5°C. Après retrait, la couche de primaire est séchée à 80°C pendant 20 minutes et on laisse refroidir pendant 15 minutes.The colored article is pretreated with a sodium hydroxide solution at 50 ° C. for 4 minutes, then immerse the article for 4 minutes in a primer composition, for example a polyurethane latex (Polyester / polyol from BAXENDEN) at 5 ° C. After withdrawal, the primer layer is dried at 80 ° C for 20 minutes and allowed to cool for 15 minutes.

    On immerge alors pendant 4 minutes la lentille dans une composition pour revêtement dur anti-abrasion à 5°C.The lens is then immersed for 4 minutes in a composition for hard abrasion-resistant coating at 5 ° C.

    Enfin, on cuit la composition de revêtement dur anti-abrasion déposée pendant 3 heures à 100°C.Finally, the abrasion-resistant hard coating composition is baked deposited for 3 hours at 100 ° C.

    On obtient ainsi un article en matériau PC coloré ayant une couche de primaire et une couche de revêtement dur anti-abrasion sur ses deux faces.An article of colored PC material is thus obtained having a primer layer and a layer of hard abrasion-resistant coating on its two sides.

    La composition pour revêtement anti-abrasion a été préparée de la façon suivante :The anti-abrasion coating composition was prepared from the following way:

    On fait tomber goutte à goutte 80,5 parties de HCl 0,1 N dans une solution contenant 224 parties de GLYMO et 120 parties de DMDES.80.5 parts of 0.1 N HCl are dropped dropwise into a solution containing 224 parts of GLYMO and 120 parts of DMDES.

    La solution est agitée 24 heures à température ambiante, puis on ajoute 718 parties de silice colloïdale à 30% dans le méthanol, 15 parties d'acétylacétonate d'aluminium et 44 parties d'éthylcellosolve. On ajoute enfin une petite quantité d'agent tensio-actif.The solution is stirred for 24 hours at room temperature, then add 718 parts of 30% colloidal silica in methanol, 15 parts aluminum acetylacetonate and 44 parts of ethylcellosolve. We add finally a small amount of surfactant.

    L'extrait sec théorique de la composition renferme environ 13% de matière solide provenant du DMDES hydrolysé.The theoretical dry extract of the composition contains about 13% solid matter from hydrolyzed DMDES.

    EXEMPLESEXAMPLES

    On a soumis des verres finis, surfacés, en homopolycarbonate de bisphénol A, fabriqués par la Société GENTEX, de puissance optique -4, - 2, 0, +4 dioptries, au traitement de coloration décrit ci-dessus.We finished, coated, homopolycarbonate glasses bisphenol A, manufactured by GENTEX, of optical power -4, - 2, 0, +4 diopters, to the coloring treatment described above.

    Après le traitement UV de photodégradation, les verres étaient ébarbés et dépoussiérés par soufflage d'air comprimé.After UV photodegradation treatment, the lenses were deburred and dusted by blowing with compressed air.

    Les verres étaient soumis au traitement UV de photodégradation ci-dessus sur les deux faces, puis au traitement de coloration par trempage de 20 minutes dans les bains ci-dessus à 94°C.The lenses were subjected to UV photodegradation treatment above on both sides, then the soaking coloring treatment 20 minutes in the above baths at 94 ° C.

    Après relargage de l'excès d'agent de coloration, rinçage à l'eau désionisée et traitement thermique de stabilisation comme décrit ci-dessus, on a déterminé le taux de transmission τv (en référence aux normes ISO/CIE 10526 : 1991 et ISO/CIE 10527 : 1991 et le projet de norme ISO/DIS 8980-3 de 1997). Pour tous les verres, le taux de transmission τv était de 17-30% correspondant à la classification 2 telle que déterminée dans le projet de norme ISO/DIS 8980-3.After release of the excess coloring agent, rinsing with deionized water and heat stabilization treatment as described above, the transmission rate τ v was determined (with reference to ISO / CIE standards 10526: 1991 and ISO / CIE 10527: 1991 and the draft ISO / DIS 8980-3 standard from 1997). For all glasses, the transmission rate τ v was 17-30% corresponding to classification 2 as determined in the draft ISO / DIS 8980-3 standard.

    Claims (39)

    1. Method for colouring a transparent article made of polycarbonate not containing polyester units and having two opposite principal faces, comprising :
      a) the photodegradation of the polycarbonate material of the transparent article by irradiation of at least one of the principal faces of the article with a UV radiation of which at least 50% of the radiation energy is a radiation having a wavelength ≤ 320 nm, to produce in the article at least one photodegraded surface layer of the polycarbonate material with a thickness of at least 1 preferably of at least 2 µm ; and
      b) placing in contact at least said principal face of the article with a colouring agent so as to diffuse the colouring agent within a thickness of at least 1 preferably of at least 2 µm of the photodegraded surface layer.
    2. Method according to claim 1, characterized in that it comprises the photodegradation by irradiation by a predetermined UV radiation of the two opposite principal faces of the article to produce in the article two photodegraded surface layers of the polycarbonate material, each having a thickness of at least 1 preferably of at least 2 µm, and in that the two opposite principal faces of the article are placed in contact with the colouring agent so as to diffuse the colouring agent within a thickness of at least 1 preferably of at least 2 µm for these two photodegraded surface layers.
    3. Method according to claims 1 or 2, characterized in that the photodegraded surface layer or layers have a thickness of 2 to 20 µm, preferably 2 to 10 µm.
    4. Method according to anyone of claims 1 to 3, characterized in that the colouring agent is diffused throughout the entire thickness of the photodegraded surface layer or layers.
    5. Method according to anyone of claims 1 to 4, characterized in that at least 60%, preferably at least 65%, of the radiation energy is a radiation having a wavelength ≤ 320 nm.
    6. Method according to anyone of claims 1 to 5, characterized in that the energy of the irradiation due to the part of the radiation with wavelength ≤ 320 nm is from 2.4 J/cm2 to 48 J/cm2, preferably 10 J/cm2 to 30 J/cm2.
    7. Method according to anyone of claims 1 to 6, characterized in that the UV radiation comprises a part of the radiation with wavelength > 320 nm and is such that the energy of the irradiation due to the part of the radiation with wavelength > 320 nm is from 0.9 J/cm2 to 15 J/cm2, preferably 2 J/cm2 to 8 J/cm2.
    8. Method according to anyone of claims 1 to 7, characterized in that the polycarbonate material is selected from the bisphenol A homopolycarbonates.
    9. Method according to anyone of claims 1 to 8, characterized in that the polycarbonate material comprises a UV absorber.
    10. Method according to anyone of claims 1 to 9, characterized in that the contact of the opposite principal face or faces of the article with the colouring agent is performed by dipping in a colouring bath containing the colouring agent.
    11. Method according to claim 10, characterized in that the colouring bath comprises a surface-active alkyl benzene sulfonate.
    12. Method according to anyone of claims 1 to 11, characterized in that it includes, after the step b), c) a thermal stabilization treatment to fix the colouring agent.
    13. Method according to claim 12, characterized in that the thermal stabilization treatment consists of heating the article to a temperature of 100 to 140°C for 1 hour or more.
    14. Method according to claim 13, characterized in that the thermal stabilization treatment consists of heating the article to 130°C for 2 hours.
    15. Method according to anyone of claims 1 to 14, characterized in that the colouring agent is selected from the azo dyes, the anthraquinone dyes and their mixtures.
    16. Method according to anyone of claims 1 to 14, characterized in that the colouring agent is selected from the photochromic compounds and their mixtures.
    17. Method according to anyone of claims 1 to 16, characterized in that it comprises the application of a layer of a hard anti-abrasion material onto at least one of the opposite principal faces of the article on which the polycarbonate material has been photodegraded.
    18. Method according to claim 17, characterized in that the hard anti-abrasion material is a (meth)acrylic resin.
    19. Method according to claim 17, characterized in that it comprises, prior to the deposit of the layer of hard anti-abrasion material, a deposit on said face of the article of a primer layer improving the adhesion of the layer of hard anti-abrasion material.
    20. Method according to claim 19, characterized in that the primer is selected from the thermoplastic polyurethanes, the thermosetting polyurethanes, the poly(meth)acrylic latexes, and the polyurethane latexes.
    21. Method according to one of claims 19 or 20, characterized in that the hard anti-abrasion material results from the curing of a hydrolysate of epoxysilane.
    22. Method according to claim 21, characterized in that the hydrolysate comprises a colloidal filler, selected from SiO2, TiO2 and Sb2O5.
    23. Method according to anyone of claims 17 to 22, characterized in that it comprises the deposit of a layer of an anti-reflection material onto the layer of hard anti-abrasion material.
    24. Method according to anyone of claims 1 to 23, characterized in that the article is an optical or ophthalmic article.
    25. Method according to claim 24, characterized in that the article is a spectacle lens.
    26. Transparent article made from polycarbonate not containing polyester units, comprising at least one photodegraded surface layer on one of the principal faces of the article and having a thickness of at least 1 preferably of at least 2 µm in which is diffused a colouring agent, within a thickness of at least 1 preferably of at least 2 µm.
    27. Transparent article according to claim 26, characterized in that it comprises two photodegraded surface layers on two opposite principal faces of the article with a thickness of at least 1 preferably of at least 2 µm in which are diffused a colouring agent, within a thickness of at least 1 preferably of at least 2 µm.
    28. Article according to claim 26 or 27, characterized in that the thickness of the photodegraded surface layer or layers is from 2 to 20 µm, preferably 2 to 10 µm.
    29. Article according to anyone of claims 26 to 28, characterized in that the colouring agent is diffused throughout the entire thickness of the photodegraded surface layer or layers.
    30. Article according to anyone of claims 26 to 29, characterized in that the polycarbonate material is a bisphenol A homopolycarbonate.
    31. Article according to anyone of claims 26 to 30, characterized in that the polycarbonate material comprises a UV absorber.
    32. Article according to anyone of claims 26 to 31, characterized in that it comprises a layer of a hard anti-abrasion material on at least the face corresponding to the photodegraded surface layer.
    33. Article according to claim 32, characterized in that it comprises a primer layer improving the adhesion between said face of the article and the layer of hard anti-abrasion material.
    34. Article according to claim 33, characterized in that the hard anti-abrasion material results from the curing of a hydrolysate of epoxysilane
    35. Article according to claim 33 or 34, characterized in that the primer layer is obtained from a thermoplastic polyurethane, a thermosetting polyurethane, a poly(meth)acrylic latex, a polyurethane latex or a mixture of these latexes.
    36. Article according to anyone of claims 26 to 35, characterized in that it comprises a layer of primer and a layer of hard anti-abrasion coating on each of its principal faces.
    37. Article according to anyone of claims 32 to 36, characterized in that it comprises an anti-reflection layer on the layer or layers of hard anti-abrasion material.
    38. Article according to anyone of claims 26 to 37, characterized in that the article is an optical or ophthalmic article.
    39. Article according to claim 38, characterized in that the article is a spectacle lens.
    EP00917114A 1999-04-08 2000-03-30 Method for colouring a transparent article made of polycarbonate and resulting article Expired - Lifetime EP1171664B1 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    FR9904409A FR2792010B1 (en) 1999-04-08 1999-04-08 PROCESS FOR COLORING A TRANSPARENT POLYCARBONATE ARTICLE AND ARTICLE OBTAINED
    FR9904409 1999-04-08
    PCT/FR2000/000792 WO2000061857A1 (en) 1999-04-08 2000-03-30 Method for colouring a transparent article made of polycarbonate and resulting article

    Publications (2)

    Publication Number Publication Date
    EP1171664A1 EP1171664A1 (en) 2002-01-16
    EP1171664B1 true EP1171664B1 (en) 2004-09-08

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    Application Number Title Priority Date Filing Date
    EP00917114A Expired - Lifetime EP1171664B1 (en) 1999-04-08 2000-03-30 Method for colouring a transparent article made of polycarbonate and resulting article

    Country Status (10)

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    US (3) US20020138921A1 (en)
    EP (1) EP1171664B1 (en)
    JP (1) JP2003500552A (en)
    AT (1) ATE275658T1 (en)
    AU (1) AU761600B2 (en)
    CA (1) CA2369737C (en)
    DE (1) DE60013582T2 (en)
    ES (1) ES2226806T3 (en)
    FR (1) FR2792010B1 (en)
    WO (1) WO2000061857A1 (en)

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    Also Published As

    Publication number Publication date
    ATE275658T1 (en) 2004-09-15
    US20040265572A1 (en) 2004-12-30
    US20020138921A1 (en) 2002-10-03
    US20050170186A1 (en) 2005-08-04
    AU3823300A (en) 2000-11-14
    JP2003500552A (en) 2003-01-07
    DE60013582T2 (en) 2005-03-31
    EP1171664A1 (en) 2002-01-16
    US6911055B2 (en) 2005-06-28
    WO2000061857A8 (en) 2002-08-08
    CA2369737A1 (en) 2000-10-19
    AU761600B2 (en) 2003-06-05
    US7179848B2 (en) 2007-02-20
    DE60013582D1 (en) 2004-10-14
    CA2369737C (en) 2010-08-10
    ES2226806T3 (en) 2005-04-01
    FR2792010A1 (en) 2000-10-13
    WO2000061857A1 (en) 2000-10-19
    FR2792010B1 (en) 2001-07-27

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